Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
  • C08G65/3348—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing nitrogen in addition to sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds

Definitions

• the present invention relates to polymers containing at least one thiuram disulfide group in their main chain.
• These polymers constitute agents having the triple function of initiator, chain transfer agent and termination agent in the radical polymerization of vinyl monomers.
• agents are commonly designated by the abbreviation "iniferter”.
• the term “macroiniferter” will be used to denote these iniferters polymers comprising a single thiuram disulfide group in their main chain, and the term “polyiniferter” to denote these iniferters polymers comprising more than one thiuram disulfide group in their main channel.
• the invention also relates to obtaining these macro- and polyiniferters from acrylic, diene or polyoxyalkylene type polymers terminated respectively at one end or at both ends of their chain by an amine group.
• the invention also relates to the block copolymers which can be obtained from these macro- and polyiniferters, and which contain vinyl or diene blocks.
• the corresponding block polymers are useful for constituting or for entering into the constitution of flame-retardant materials.
• the present invention results from new developments in research in the field of radical polymerization using, as iniferters, compounds comprising one or more thiuram disulfide groups, the vinyl or diene polymer sequences being inserted between the two sulfur a thiurame group.
• the invention makes it possible to obtain block vinyl polymers constituted by hard sequences alternating with soft sequences, or alternatively sequences hydrophilic alternating with hydrophobic sequences (amphiphilic copolymers).
• alkyl methacrylates and acrylates the alkyl group of which contains, for example, from 1 to 8 carbon atoms, vinyl aromatic hydrocarbons, unsaturated nitriles, cyanoethyl acrylates, acrylamide, lower hydroxyalkyl acrylates and methacrylates, acrylic acid and methacrylic acid, maleic anhydride and maleimides substituted with alkyl or aryl groups.
• diene monomers there may be mentioned, among others, butadiene, isoprene, 1,3-pentadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,9 -decadiene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 2-alkyl-2,5-norbornadienes, 5-ethylidene-2-norbornene, 5- (2-propenyl) - 2-norbornene, 5- (5-hexenyl) -2-norbornene, 1,5-cyclooctadiene, bicyclo [2,2,2] octa-2,5-diene, cyclopentadiene, 4,7,8 , 9-tetrahydroindene and isopropylidene tetrahydroindene.
• polyoxyalkylene block P2 it can be chosen from the sequences of the formulas: j being from 1 to 1000, preferably from 1 to 200.
• polyester sequence P2 is in particular a sequence of formula: R18, R19 and k being as defined above.
• the polyamide P2 sequence is in particular a sequence of formula: R22 and m being as defined above.
• the alkyl groups falling within the definition of formulas (I) and (II) above are in particular C1-C12 alkyl groups, in particular C1-C6.
• the cycloalkyl groups are in particular C3-C12 cycloalkyl groups, in particular C5-C7; and the aryl groups are, for example, phenyl or naphthyl groups.
• the heteroatoms are in particular O or S.
• a group can signify an alkyl, cycloalkyl or aryl residue, or an alkylene, cycloalkylene or arylene residue, the combinations of at least two of these are also understood radicals, for example an aralkyl and alkaryl radical.
• G can represent, among other things, a remainder - (CH2) q -, q being 1 to 6, or a remainder the group can represent, among others,
• the polymerization is carried out, either in bulk or in a solvent medium, at a temperature of, for example, between about 30 and 160 ° C.
• the solvent is especially chosen from those capable of dissolving the polymer chain, for example, tetrahydrofuran, toluene, ethanol and their mixtures.
• the oxidizing agent used in the second step is chosen, for example, from iodine, hydrogen peroxide, alkali metal hypochlorites and alkyl and aryl hydroperoxides.
• a substantially equimolar ratio of the polymer (IV) or (IV ') to CS IV can be used, the reaction possibly being carried out in the presence of a tertiary amine (for example, pyridine or triethylamine), about 1 mole per mole of the polymer (IV) or about 2 moles per mole of the polymer (IV ').
• a tertiary amine for example, pyridine or triethylamine
• the oxidizing agent is added, for example, at a rate of approximately 1 mole per mole of CS2.
• reaction of this second step is exothermic and its exothermicity is controlled by any known means. Furthermore, it is preferably carried out in a solvent medium, CS2 being able to act as a solvent.
• a substantially equimolar ratio of the compound (V) or (V ′) to CS2 can be used, the reaction possibly being carried out in the presence of a tertiary amine, at a rate of approximately 1 mole per mole of the compound ( V) or about 2 moles per mole of compound (V ′).
• the oxidizing agent is added, for example, at the rate of approximately 1 mole of CS2.
• the polymerization is carried out, either in bulk or in a solvent medium, the latter being in particular chosen from those capable of dissolving the compound (VI), for example, toluene, tetrahydrofuran, ethanol and their mixtures, at a temperature between about 30 and 160 ° C.
• a molar ratio of compound (VII) to CS2 is preferably used which is substantially 1 to 2, the reaction possibly being carried out in the presence of a tertiary amine, at a rate of approximately 1 mole per mole of CS2.
• the oxidizing agent is added, for example, at a rate of approximately 1 mole per mole of CS2.
• the reaction is preferably carried out at a temperature of approximately 5 to approximately 30 ° C., in a solvent medium, the solvent being chosen in particular from aromatic solvents, such as toluene.
• the reaction is preferably carried out at a temperature of about 20 to 90 ° C, in the presence of a non-reactive solvent, such as anhydrous acetonitrile.
• a non-reactive solvent such as anhydrous acetonitrile.
• a substantially equimolar ratio of the polymer (XI) to CS2 is preferably used, the reaction possibly being carried out in the presence of a tertiary amine, at a rate of approximately 1 mole per mole of the polymer (XI).
• the oxidizing agent is added, for example, at a rate of approximately 1 mole per mole of CS2.
• the reaction is preferably carried out at a temperature of between approximately 5 and 30 ° C., in a solvent medium, the latter being chosen in particular from aromatic solvents, such as toluene.
• the reaction is preferably carried out at a temperature of about 20 to about 90 ° C, in the presence of a non-reactive solvent, such as anhydrous acetonitrile.
• a non-reactive solvent such as anhydrous acetonitrile.
• a molar ratio of the polymer (XIV) to CS2 preferably of 1: 2 is preferably used, the reaction possibly being carried out in the presence of a tertiary amine, at a rate of approximately 1 mole per mole of CS2.
• the oxidizing agent is added, for example, at a rate of approximately 1 mole per mole of CS2.
• the present invention also relates to a process for the manufacture of a polymer of formula (I) where P1 is a polyamide block or a polyester block obtained from a polyester terminated by an acid or ester function, characterized in that one uses , as starting polymer, a polyamide terminated with a secondary amine function, or else a polyamide or a polyester terminated with an acid or ester function which is reacted with an excess of the compound (X) or (X ⁇ ) or with a compound (V) or (V ′), to obtain, if necessary after hydrolysis, a P1-AH polymer, which is reacted with carbon disulfide in the presence of at least one oxidizing agent or by adding this agent after the reaction.
• the present invention also relates to a process for the manufacture of a polymer of formula (II) where P2 is a polyamide block or a polyester block derived of a polyester terminated with acid or ester functions, characterized in that the acid or ester endings of the starting polyester are transformed, and if appropriate the acid or ester endings of the starting polyamide, by reaction with an excess of the compound (X) or (X ⁇ ) or with a compound (V) or (V ′), A representing to obtain, if necessary after hydrolysis, a HA-P2-AH polymer, which is reacted with carbon disulfide in the presence of at least one oxidizing agent or by adding this agent after the reaction.
• the reaction is carried out, preferably at a temperature of between approximately 5 ° C. and 30 ° C., in a solvent medium, the solvent being chosen in particular from those known to those skilled in the art who allow the polyester or polyamide sequences to be dissolved.
• a substantially equimolar ratio of the polymer P1-AH to CS2 the reaction can be carried out in the presence of a tertiary amine, at a rate of 1 mole per mole of the polymer P1-AH, and the oxidizing agent being added, for example, in an amount of approximately 1 mole per mole of CS2; and, in the second case, a ratio of the HA-P2-AH to CS2 polymer is preferably used, of approximately 1: 2, the reaction possibly being carried out in the presence of a tertiary amine, at a rate of 1 mol per mole of the polymer HA-P2-AH, and the oxidizing agent being added, for example, in an amount of approximately 1 mole per mole of CS2.
• the present invention also relates to triblock copolymers of formula: PA-PB-PA in which PA is a vinyl, diene, polyoxyalkylene, polyester or polyamide block, and PB is a vinyl or diene polymer block, different from PA when PA is also a vinyl or diene sequence, PA being from the macroiniferter of formula (I).
• the invention also relates to a process for the production of these triblock copolymers, characterized in that the polymerization of a monomer B is carried out in the presence of a compound of formula (I), at a temperature of 50 to 160 ° C approximately, to obtain the polymer of formula: or
• the present invention also relates to bis-sequenced copolymers of formula: in which PA and PB are different vinyl or diene blocks or else PA is a polyoxyalkylene, polyester or polyamide block, and PB a vinyl or diene block, PA being derived from the polymer of formula (II) as defined above, with z being from 2 to 25, in particular from 2 to 10.
• the invention also relates to a process for the manufacture of these block copolymers, characterized in that the polymerization of a monomer B is carried out, in the presence of a compound of formula (II), at a temperature of 50 to 160 ° C approximately to obtain the polymer of formula:
• the PB sequence is inserted between the disulphide functions of thiuram in formula (II) as developed above.
• the POE-Cl obtained (20 g; 0.04 mole) is treated with 15 ml of dry acetonitrile and 0.2 mole of piperazine. The system is reacted at 85 ° C. for 8 hours, cooled and 150 ml of distilled toluene are added thereto. The solution is filtered and the polymer is recovered by precipitation in ether.
• the thiocarbamylation is carried out as follows: 15 g of the above polymer are dissolved in 100 ml of toluene; 1 ml of triethylamine and 1 ml of CS2 are added. A solution of I2 in toluene is added before the end point. After stirring the solution at room temperature for 1 hour, it is filtered and the expected macroiniferter is precipitated in ether and dried under vacuum at room temperature.
• the macroiniferter is characterized by GPC: its molecular mass Mw is 14,000.
• Example 3 The procedure was as in Example 3, but starting from an HO-POE-OH of molecular mass 8,000.
• Tables 1 to 4 illustrate the conditions of synthesis of tri-sequenced PA-PB-PA or bisequenced (PA-PB) z copolymers using the macroiniferters of Examples 1 and 2 respectively, and the polyiniferter of Example 3, as well than the results obtained.
• the macroiniferter is dissolved in 10 ml of monomer in a Pyrex glass tube and sealed under vacuum. The polymerization is carried out at 80-85 ° C for 24 hours. The polymer is dissolved in THF and precipitated in methanol. The unused macroiniferter is eliminated by dissolution. The copolymer is recovered by filtration and dried under vacuum. It is characterized by GPC (molecular mass) and by NMR (composition).
• the procedure is identical to that used for the preparation of triblock polymers, except that the polymerization times can range up to 48-60 hours, and that toluene must be used as solvent.
• the copolymer is precipitated in heptane and it is purified by cold methanol. It is characterized by GPC (molecular mass) and by NMR (composition).
• the transfer agent namely BAET hydrochloride (Aldrich) is purified by vacuum distillation.
• the synthesis of the corresponding salt is carried out in a solution of distilled ether by adding, in molar excess, aqueous hydrochloric acid.
• the ether is then removed by decantation.
• the salt is extracted using chloroform, the mixture being dried over sodium sulfate. After filtration, then evaporation of the chloroform under vacuum, the salt is recovered.
• the polymerization takes place at 60 ° C. in sealed tubes and under vacuum, the reaction mixture having been previously cooled in a mixture of dry ice and isopropanol, degassed under vacuum, then left at room temperature, and this, several times. Diluted in a THF solution, the polymer obtained is precipitated in methanol (in the case where the monomer is St or MMA), or in a 50-50 mixture of water and methanol (in the case where the monomer is l 'EA). It is finally dried under vacuum at 50 ° C for 3-4 hours.
• Table 5 illustrates the conditions for the synthesis of various polymers of this type.
• DAET was released from its hydrochloride by treatment of its aqueous solution with a slight excess of NaOH.
• the released amine was extracted with ether, dried; the ether was evaporated, and the residue, distilled in vacuo.
• MEP hydrochloride is prepared by treatment of an alcoholic solution with HCl, then by precipitation in ether.
• Table 6 illustrates the conditions for the synthesis of various polymers of this type.
• the starting polymer is dissolved at 15% by weight in chloroform.
• Triethylamine (Aldrich) and carbon disulfide (Aldrich) are then added in minimum molar quantities for CS2 and twice molar for triethylamine.
• the mixture is stirred for about 30 minutes at room temperature.
• the addition of I2 leads to the oxidation of sulfur and to the synthesis of the macroiniferter.
• the reaction by-products are separated from the starting polymer by washing with water if the starting polymer is a PEA, the macroiniferter PEA being recovered after evaporation in vacuo of the chloroform. In the case of PMMA and PSt, the macroiniferter is recovered directly in methanol and dried under vacuum.
• the starting polymer is stirred with CS2, in an amount of 1 mole, in the presence of one mole of triethylamine per mole of starting polymer or of CS2, at room temperature, in chloroform. Then, the oxidation is carried out using an iodine solution in HCCl3.
• PEA-PMMA-PEA and PEA-PSt-PEA PEA-PMMA-PEA and PEA-PSt-PEA
• a solution polymerization is carried out, the macroiniferter being of the type of that of Example 59.
• the distilled THF is used as solvent in a proportion of 50 to 100% by volume relative to the monomers MAM and St, this ratio increasing with the molar mass of the copolymerized macroiniferter.
• 10 ml of MMA or ST are added.
• the polymerization is carried out at a temperature of 80 ° C., for 48 hours, in sealed tubes, under vacuum, and degassed several times according to the procedure described for the synthesis of the polymer terminated by an amine function.
• the triblock polymer obtained is diluted in a THF solution, then purified by precipitation in methanol.
• Example 89 The same synthesis is carried out as in Example 89, but using styrene as the monomer.
• Example 91 The procedure is as in Example 91, but the polyiniferter of Example 90 and MMA is used as the added monomer; in this case, the extraction of the block copolymer is carried out using cyclohexane to remove the excess polyiniferter.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Polymerisation Methods In General (AREA)
• Polyamides (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Graft Or Block Polymers (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Polyethers (AREA)
• Polymerization Catalysts (AREA)
• Polyesters Or Polycarbonates (AREA)
• Macromonomer-Based Addition Polymer (AREA)

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• 1989
  • 1989-09-14 FR FR8912061A patent/FR2651781B1/fr not_active Expired - Fee Related
• 1990
  • 1990-09-04 ES ES90402427T patent/ES2062451T3/es not_active Expired - Lifetime
  • 1990-09-04 AT AT90402427T patent/ATE101165T1/de not_active IP Right Cessation
  • 1990-09-04 EP EP90402427A patent/EP0418118B1/fr not_active Expired - Lifetime
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  • 1990-09-04 DK DK90402427.0T patent/DK0418118T3/da active
  • 1990-09-13 CA CA002025251A patent/CA2025251A1/fr not_active Abandoned
  • 1990-09-14 JP JP2245959A patent/JPH0662700B2/ja not_active Expired - Lifetime
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  • 1990-09-14 KR KR1019900014562A patent/KR930007690B1/ko not_active IP Right Cessation
• 1995
  • 1995-12-18 US US08/574,143 patent/US5658986A/en not_active Expired - Fee Related

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